CN103140570B - Fischer-tropsch catalyst regeneration - Google Patents
Fischer-tropsch catalyst regeneration Download PDFInfo
- Publication number
- CN103140570B CN103140570B CN201180047764.0A CN201180047764A CN103140570B CN 103140570 B CN103140570 B CN 103140570B CN 201180047764 A CN201180047764 A CN 201180047764A CN 103140570 B CN103140570 B CN 103140570B
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- catalyst
- regeneration
- reactor
- aforementioned method
- inactivation
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Classifications
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
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- C—CHEMISTRY; METALLURGY
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- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C07C2523/42—Platinum
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Abstract
Make a method for the catalyst regeneration of the inactivation from fischer-tropsch reactor, described catalyst is supported cobalt catalysts.Said method comprising the steps of: take out step, wherein, the catalyst of a part of inactivation is taken out together with liquid hydrocarbon from reactor; Concentration step, wherein, improves the concentration of catalyst in liquid hydrocarbon; Calcining step, wherein, makes the carbon monoxide-olefin polymeric experience oxidizing gas of described inactivation, the carbonaceous material be included in the catalyst of described inactivation to be oxidized into the gaseous oxygen compound of the component of carbonaceous material; With reactivation step, wherein, by the carbon monoxide-olefin polymeric reactivation of described inactivation, to produce the catalyst of regeneration.
Description
Technical field
The present invention relates to loaded catalyst and their application in Fischer-Tropsch (FT) synthetic reaction, more specifically, the present invention relates to the renovation process of used catalyst.
Background technology
Be liquid hydrocarbon (" gas is converted into liquid " or " GTL(Synthetic Oil Production from Natural Gas) by conversion of natural gas " process) based on 3 step programs, this program is made up of following: 1) synthesis gas is produced; 2) by Synthetic holography that FT synthesizes; With 3) upgrading FT product (wax and naphtha/distillation) to end product.
Transformation of synthetic gas (be the mixture of CO and hydrogen, may also containing basic inert component, as CO
2, nitrogen and methane) Fischer-Tropsch reaction industrially operate on the catalyst containing active metal Fe or Co.Iron catalyst is most suitable for having low H
2the synthesis gas of/CO ratio (<1.2), such as, derive from the synthesis gas of coal or other heavy hydrocarbon feedstocks, wherein this ratio significantly lower than FT reaction consumption than (2.0-2.1).The present invention relates to the catalyst based on Co, particularly, load type Co is catalyst based.Multi-products by FT-reaction preparation, but derives from the cobalt of load, and primary product is to upgrade to the long chain hydrocarbon of product as diesel fuel and petroleum chemicals naphtha further.Accessory substance can comprise alkene and oxygenate (oxygenates).
In order to realize enough catalytic activitys, in catalyst carrier (being commonly referred to carrier mass), disperse Co traditionally.Adopt in this way, the Co of major part exposes as surface atom, and wherein, this surface atom can react.
Load type cobalt-base catalyst is the preferred catalyst for FT synthesis.The most important character of cobalt FT catalyst be active, usually for the selective of C5 and heavier product (that is, C5+) and the resistance to inactivation.The physical strength of catalyst and carrier and chemical robustness are also conclusive.Usually, when deployed, catalysing area is deployed in slurry types fluid bed or fixed bed reactors, but has proposed other type of reactor, as microstructured reactor.In slurry-phase reactor, average catalyst particle size can be 20-200 μm.
All industrially operate catalyst experience inactivation, that is, through time stream on (TOS) (time-on-stream) catalyst activity reduction, may seldom make an exception.Usually, after the operation (usual 0.5-5) of some times, catalyst must more renew.For some reactions experiencing very rapid deactivation, need continuous or semicontinuous reconstituted form.For the FCC (fluid catalytic cracking) in the oil plant that coke after several seconds operation must be burnt especially like this.But continuous inactivation also regards that impurity picks up the result of (pick-up) from oil as.At catalytic reforming to obtain in gasoline, active Pt/Re or Pt/Sn system must by carrier again dispersed activity platinum regenerate regularly.For cobalt Fischer-Tropsch catalysts, at Applied Catalysis A:General, the 354th volume, 102-110 page, reports the research of the catalyst of the inactivation operated in slurry bubble column in 2009.Main conclusion is because the richness deposition of carbon causes long-term inactivation.
Use cobalt type catalyst, particularly when using slurry-phase reactor type operations, the appropriateness about catalyst regeneration experiences (Moderate experience) and is obtained by the operation of full-scale industry (2000-20000bpd production) or half industrial size fischer-tropsch reactor (200-2000bpd).Catalyst contains expensive cobalt, and usually also containing external promoter, as platinum or rhenium.These are extremely expensive, and due to the large scale of modern GTL equipment, also can form the major part of world production.After off-load, the therefore mandatory recovery of the catalyst of inactivation metal as much as possible.These can be used for other Catalyst Production.Metal recovery is generally the process of the complexity relating to multiple step (as chemical extraction or complexing).In addition, catalyst itself is certainly destroyed.Therefore, more attracting scheme makes catalyst regeneration for further use.
Regeneration existence two kinds of main paties, in-situ regeneration and device outer (ex situ) regeneration, refer to inner at FT-reactor itself or be separated with reactor.Original position means stopping FT-reaction, and about gas composition, uses special condition, and possible temperature and pressure.In the context of the present invention, we represent that the special revived structure of original position for use partial reaction body to amass in cyclic regeneration, or by getting effluent from the slurry or fluidized-bed reactor that are exposed to regeneration condition and again disposing continuously in the reactor and carry out identical operation.Although in-situ regeneration has some advantage, serious obstruction is that the condition that can use lacks flexibility.Such as, in slurry FT-reactor, people can not use temperature and/or the oxygen of rising, not destroy liquid phase, this is that slurry operates possible serious consequence.In addition, design and the operation of reactor are very complicated, and its degree makes in-situ regeneration unrealistic.
Use hydrogen or the gas that is rich in hydrogen to be the option proposed, for example, see EP0319625, it is disclosed that the hydrogen situ regeneration cobalt FT-catalyst that flows at low temperatures.But the efficiency of such regeneration is problematic, because the heavy hydrocarbon of deposition can not be removed to required degree.The present invention relates to the FT catalyst that a kind of simple and highly effective mode carrys out ex-situ regeneration inactivation." ex-situ regeneration " is interpreted as catalyst to dispose removing from reactor, such as, fluid separation applications in operating with slurry, and is exposed to special reproducer.
In WO2008/139407, describe a kind of method of ex-situ regeneration.First dewaxing treatment is experienced, oxidation processes under 4-30 bar pressure, then reduction treatment with the cobalt FT catalyst crossed.Dewaxing is described as hydrogenolysis, solvent wash or extraction, or their combination.Regrettably, in WO2008/139407, do not show the effect of regeneration itself, during being only presented at oxidation stage, use the relative result of different pressures.
Summary of the invention
According to the present invention, provide a kind of method making the catalyst regeneration of inactivation from fischer-tropsch reactor, described catalyst is supported cobalt catalysts, said method comprising the steps of:
-take out step, wherein, the catalyst of a part of inactivation is taken out together with liquid hydrocarbon from reactor;
-concentration step, wherein, lower than at the temperature of 220 DEG C, improving the concentration of catalyst in liquid hydrocarbon, is the carbon monoxide-olefin polymeric that benchmark contains the first inactivation of the catalyst granules of 45-99.5% to produce with dry weight;
-the first calcining step, wherein, at the temperature of 150-600 DEG C of scope, make the carbon monoxide-olefin polymeric experience oxidizing gas of described first inactivation, arrange the gaseous oxygen compound carbonaceous material be included in the catalyst of described inactivation being oxidized into the component of carbonaceous material, to produce the carbon monoxide-olefin polymeric of the second inactivation;
-reactivation step, wherein, by the carbon monoxide-olefin polymeric reactivation of described second inactivation, to produce the catalyst of regeneration.
In this manual, term carbonaceous material on a catalyst or carbon-containing sediment refer to poor hydrogen and in the operating condition usually can not from the material of the carbon containing of catalyst surface removing and hydrocarbon compounds.Such carbonaceous material comprises pure carbon, graphite, coke, Merlon (polycarbon), the aromatic compounds condensed, alkene and long chain hydrocarbon, and also can comprise oxygen in their preparation (formulations).
Although it should be understood that and be essentially hydrocarbon taking out in step the liquid taken out, can be oxygenate, such as acid, alcohol etc. up to a few percent.
Preferably, reactor is slurry bubble bed bioreactor, wherein, by H
2be supplied in the slurry in reactor with CO gas, described pulp bales is containing catalyst, and this catalyst is suspended in containing H
2with in the liquid hydrocarbon of the product of CO, at least partly by being supplied to the gas motion of slurry, make described catalyst keep being suspended in slurry, and described taking-up step comprise take out a part of slurry from reactor.
Take out step can carry out continuously or intermittently.In operation, the catalyst granules of reactor inevitably containing different conditions activation.Usually, in practice, reactor may containing the total quantity in stock of catalyst of 300-1200 ton, and every day wherein about 1-10 ton may be removed for reactivation.
Therefore, preferably, take dry weight as benchmark, the amount of taking out the catalyst being used for reactivation accounts for the 0.01-10 % by weight of the total quantity in stock of described catalyst, preferred 0.1-5 % by weight, more preferably 0.2-2 % by weight.Preferably, at least 60%, more preferably at least 80%, also more preferably at least 95% taking-up catalyst regeneration and be back to reactor.
Usually, when carry out F-T synthetic reaction in slurry bubble bed bioreactor, in the residence time destribution of the catalyst granules of described regeneration, wherein, the catalyst inventory of 80% uses 1 week-10 years in the reactor, preferably 1 month-5 years, the more preferably time period of 2 months-2 years.
Preferably, carry out concentration step, to produce 70-99.5 % by weight, preferred 75-90 % by weight, or the catalyst content of 95-99 % by weight.Preferably, carry out concentration step, to produce wax content at 1-55 % by weight, preferred 2-45 % by weight, the carbon monoxide-olefin polymeric of described first inactivation more preferably in 3-30 % by weight scope.More than one concentration step can be there is.
Preferably, concentration step comprise be selected from sedimentation, filtration, Magnetic Isolation, hydrocyclone be separated and solvent-extracted operation.This operation can comprise sedimentation, then removes a part of liquid hydrocarbon, or can comprise solvent extraction, and wherein solvent is hydrocarbon, is preferably small amount of liquids F-T product and/or paraffinic naphtha.Solvent can be joined in hydrocyclone.Preferably, described or each concentration step, lower than 200 DEG C, carries out more preferably less than at the temperature of 180 DEG C.Preferably, the par of the carbon atom of the hydrocarbon molecule in the carbon monoxide-olefin polymeric of described first inactivation is significantly lower than the hydrocarbon molecule in slurry-phase reactor.Preferably, this quantity is less than 70% of the quantity of the carbon atom of the hydrocarbon molecule in slurry-phase reactor, is preferably the 25-50% of the quantity of the carbon atom of the hydrocarbon molecule in slurry-phase reactor.
Aptly, the oxidizing gas in the first calcining step is oxygen-containing gas, is preferably air.Preferably, the oxygen content of oxygen-containing gas is 2-30 volume %, is more preferably 5-21 volume %.Preferably, the first calcining step comprises the carbon monoxide-olefin polymeric of described first inactivation is delivered to calcining furnace, and described calcining furnace has the temperature of at least 150 DEG C, preferably at least 250 DEG C.First calcining step can at 150-600 DEG C, preferred 250-400 DEG C, more preferably carries out at the maintenance temperature of 270-350 DEG C.
Preferably, the time that the first calcining step carries out is 0.01-10 hour, preferred 0.1-2 hours window.It can carry out in rotary calciner, static kiln or fixed bed or fluid bed.Preferably, carry out the first calcining step, and arrange so that the content of the carbonaceous material in catalyst is reduced to <1 % by weight.
Other calcining step or multiple step can be there is, such as, for removing deposits of coke.Condition can be different from the condition in the first calcining step, such as, at higher maintenance temperature.
Unexpectedly, the present inventor finds that highly effective regeneration can be carried out in the process not using dewaxing, and wherein, oxidation (calcining) is carried out under atmospheric pressure or modest pressure.In addition, the selective experience of C5+ is significantly improved.Calcine remarkable simplification process at atmospheric pressure or close to carrying out under atmospheric pressure, and conventional means of calcination can be used.These comprise rotary calciner and static kiln calcining furnace, and comprise other type, such as swing, moving bed, fluid bed and continuous fluid bed calcinator.In the context of this article, calcining refers to heat treatment at elevated temperatures.Usual use air carries out under oxidative conditions, but also can use inert gas or other gas composition.In order to avoid wax a large amount of during calcining evaporation, decompose or oxidation, the catalyst content in catalyst/wax mixture can concentrate.This realizes by any suitable means, comprises sedimentation, filtration, use hydrocyclone and Magnetic Isolation, at the temperature preferably at least partially in wax melting.
Preferably, reactivation step comprises the process of use reducing gas, and preferred reducing gas contains hydrogen, and more preferably essence is made up of hydrogen.Preferably, reactivation step is at 200-600 DEG C, and preferred 250-500 DEG C, carries out at the one or more maintenance temperature more preferably within the scope of 300-450 DEG C.
Preferably, after reactivation step, the catalyst of regeneration is incorporated in reactor again.Preferably, before it being incorporated into again in reactor, the catalyst of regeneration being mixed with liquid hydrocarbon, preferably mixes with fraction F-T product.Selectively, before it is introduced again, after remove most of catalyst granules from slurry, the catalyst of regeneration is mixed with the liquid hydrocarbon taken out as slurry from reactor.
Alternatively step, it is possible that use organic liquid (being generally hydrocarbon) washing catalyst before calcination.But, do not need to remove all wax, and calcining can occur under environmental pressure or low-pressure.Optimum is use the hydrocarbon-fraction washing deriving from Fischer-Tropsch process itself, and this is owing to easily obtaining in factory.The naphtha mainly with the carbon number of C5-C15 is suitable, but any liquid distillate that can remove most of wax is all right.Washing itself can be carried out in any suitable groove or device, but particularly advantageously applies hydrocyclone.If joined by naphtha in hydrocyclone, the catalyst stream of high enrichment can realize, and for further process, is generally calcining.Drying/evaporation can be carried out before calcination, to remove excessive naphtha.
In Fischer-Tropsch process, before further processing, for remaining catalyst, process and the elementary hydrocarbon products of purification of liquid are necessary.Catalyst can be very thin particle form, such as size range <20 μm, or <5 μm or <1 μm, or is soluble component." fines process (finesmanagement) " system like this can comprise various technology, as sedimentation, filtration, use hydrocyclone, magnetic methods and chemical precipitation or other suitable means.Use these measures any, by guaranteeing that the Primary product carrying out autoreactor is in the reactor containing some catalyst, being used for regeneration from liquid reactor separating catalyst advantageously can be treated as entirety with described fines.In this case, first larger particle will be separated and experience regeneration.
Therefore, described method also can comprise the step by using filter, net or sieve to be reduced in the level of fines in the catalyst of regeneration in the gas flow, comprises and uses fluid bed or air screening installation.Preferably, in the catalyst of the regeneration again introduced, content lower than the thin catalyst granules of the fractions of 20 μm is less than 3 % by weight, content preferably lower than the thin catalyst granules of the fraction of 10 μm is less than 0.5 % by weight, and the content most preferably lower than the thin catalyst granules of the fraction of 10 μm is less than 0.2 % by weight.
Suitable carrier mass for catalyst comprises titanium dioxide, silica and aluminium oxide and various metal oxide and modified aluminas and their mixture.These carriers can be shaping by different way, and to obtain suitable form, this depends on type of reactor to be employed, and such as, by the spray-drying technique of suitable solution, to obtain the substantially spherical particle with appropriate size, such as 80% 30-200 μm of scope.After spray-drying, material is at high temperature calcined, to obtain suitable crystalline size and pore structure.
Modified aluminas comprises by adding stabilizing agent, using the alumina support of silane and other silicon compound process and various acid or alkali addition or washing procedure modification.Make alumina modified a kind of mode for add bivalent metallic compound in aluminium oxide or alumina precursor, then high-temperature process.High-temperature process is preferably carried out at 700-1300 DEG C, more preferably 900-1250 DEG C.Suitable bivalent metallic compound comprises nickel, zinc and magnesium and forms other metal of spinelle with aluminium oxide.Optionally, promoter can be added, and rhenium is the well-known promoter for cobalt Fischer-Tropsch catalysts.Other promoter except rhenium can be adopted, especially, platinum, iridium or ruthenium.Also can add the second promoter, other compound that the oxide mixture of such as lanthanum-oxides or lanthanide series or be difficult to reduces.
Therefore, in a preferred embodiment, catalyst comprises the cobalt of load on the carrier be substantially made up of aluminium oxide or modified aluminas.Preferably, before use cobalt initial impregnation, catalyst support material is gama-alumina, and it can use 2-valency source metal to flood, and calcines, to form spinelle.Preferably, 2-valency metal is nickel or zinc, and its amount is greater than 10 % by weight of the catalyst of final reduction.Preferably, carry out at the temperature of this calcination operation within the scope of 900 DEG C-1250 DEG C.
Preferably, after regeneration, in the cobalt content of the catalyst of regeneration, the no more than amount of 5 % by weight is different from the new catalyst after reduction, is preferably less than the amount of 2 % by weight, and the amount being more preferably less than 0.5 % by weight is different from the new catalyst after reduction.Catalyst can contain promoter, preferred rhenium or platinum.Preferably, before reactivation step, comprise the specific area of the new oxide of the cobalt on modified support and the catalyst of regeneration up to 150m
2/ g or up to 80m
2/ g, and the new and pore volume of the catalyst of regeneration of oxide form is 0.05-0.5cm
3/ g, preferred 0.1-0.4cm/g.Before recycling, the catalyst of regeneration can use the coating protection of wax.
WO2005/072866 discloses a kind of method of producing alumina base loaded catalyst, said method comprising the steps of: the first impregnation steps, and wherein, initial oxidation alumina supporter material is flooded by the 2-valency source metal that can form spinel compound with aluminium oxide; First calcining step, wherein, by the temperature lower calcination of the alumina support material of described dipping at least 550 DEG C, with the alumina support material of production modification; Second impregnation steps, wherein, described modified aluminium oxide supports material catalyzed active metal source dipping; With the second calcining step, wherein, by the temperature lower calcination of the modified support material of described dipping at least 150 DEG C.Then reduction step subsequently, to activate cobalt.
The research display of this technology, in the present invention, 2-valency source metal preferably comprises nickel or zinc, and its amount is greater than 5 % by weight of the catalyst of final reduction, is preferably greater than 10 % by weight.Preferably, initial catalyst agent carrier is aluminium oxide, more preferably substantially comprises gama-alumina.Preferably, the specific area of initial oxidation alumina supporter material is at 100-400m
2/ g scope, and pore volume is greater than 0.3cm
3/ g, is preferably greater than 0.5cm
3/ g.Aptly, after the first calcining step, the surface area of modified aluminium oxide supports is 20-80m
2/ g.
Before impregnation, catalyst carrier can be calcined in advance at about 500 DEG C.In the present invention, flood in one step in a kind of suitable mode of supported on carriers active metal and promoter, but also can adopt multiple step, be flooded by the mixed aqueous solution of suitable slaine (be generally cobalt nitrate and perrhenic acid or selectively ammonium perrhenate).Usually dipping technique used is that hole is filled or " just wet impregnation " method, wherein, is mixed by solution with dry support, until hole is filled.Being defined in of terminal of the method may be slightly different between laboratory and laboratory, and the catalyst therefore flooded can have outward appearance or the viscosity snow core outward appearance of bone dry.But, when adopting first wet impregnation method, there is any free-pouring liquid in no instance.
Plurality of optional is selected dipping method and is used optional solvent and chemicals to be known in the art, but use the catalyst shown in an embodiment of the present invention, preferred method relates to use cobalt nitrate (Co (NO
3)
2* 6H
2and perrhenic acid (HReO O)
4) the water just wet impregnation of solution.Possible selectable comprising uses cobalt acetate, cobalt carbonate, halo cobalt, carbonyl cobalt, cobalt oxalate, cobalt phosphate, organic cobalt compounds, ammino-complex (ammine complexes), ammonium perrhenate, halo rhenium, rhenium carbonyl, Industrial Metal salting liquid, organic solvent and inorganic or organic bond etc.Solution also can comprise pH adjusting agent, complexing agent, surfactant and in some manner in other compound of impact dipping and step below.Therefore, ammonia or urea can be used.
In addition, except just wet impregnation, dipping technique also can comprise all available methods, such as, precipitate, use remaining liq from impregnating slurry, chemical vapour desposition etc.As everyone knows, dipping method can affect the dispersion of active metal (cobalt), therefore affects catalytic activity.In addition, prepare at carrier and in a subsequent step, large concern should be adopted to limit the concentration of the anticatalyst pest of Fischer-Tropsch reaction to acceptable level.Such murder by poisoning thing generally includes alkali metal, alkaline-earth metal, sulphur and chloride.
According to one of Kaolinite Preparation of Catalyst suitable program, after the solution impregnation of alumina carrier material using cobalt compound, it is dry at such as 80-120 DEG C, with from catalyst pores except anhydrating, and at the relatively low temperature lower calcination 2-16 hour of 200-500 DEG C (at such as 300 DEG C).By reduction step, cobalt is activated subsequently, usually at about 200-600 DEG C, at preferred 300-450 DEG C, under the pressure that atmospheric pressure-30 clings to, use reducing gas (such as hydrogen) to process catalyst.But preferred reduction temperature will depend on actual carrier used and wherein prepare the mode of described oxide catalyst.
Sometimes can aptly reduction step being divided into other reduction step or comprising polishing, by using the hydrogen of low concentration in inert carrier gas, such as, being less than 5 volume %.Polishing step can reduce the residual volume of the component (such as nitrate) from dipping.CO also can be used as reducing gas, independent or and H
2mixing, and by reducing gas and inert gas (such as nitrogen, rare gas) or steam, and can should use suitable temperature and pressure.
If fluidized-bed reactor is used for activation, the recirculation of reducibility gas at least partially and the total overvoltage of slight atmospheric pressure can be used aptly, to realize suitable air-flow.Also can use the gross pressure of rising, such as, up to 8 bar or higher, or even fischer-tropsch reactor pressure.Existence and the character of promoter are depended in the selection of reduction temperature strongly.Well-known Re is highly effective as promoter, to realize high reproducibility under suitable reduction temperature.
During in the past 20 years, in more than one piece patent and article, describe the activation procedure of optimization.US4670414 describes and makes the activity of the raising of the catalyst of the carbonyl cobalt-dipping on aluminium oxide or silica as follows: their experience (A) are reduced in hydrogen, (B) be oxidized in oxygen-containing gas, (C) reduce in hydrogen, claim and this significantly improves the performance of catalyst at Fiscber-Tropscb synthesis.US4729981 describes on the catalyst containing cobalt or nickel of the identical method of use in refractory metal oxide carriers.US2004/0127585 describe common charging ppm measure carbon monoxide and reducing gas with reduce from slurry loss of liquid and produce methane.US7045554 describes the less more unstable metallic crystal inactivation how low-level oxygen makes to be present in catalyst substrates, therefore obtains more stable catalyst.
Preferably, the specific area (use modified support) of the oxide catalyst (that is, the catalyst after firing still before reduction) of the preparation of the present invention of cobalt oxide is comprised up to 150m
2/ g or up to 80m
2/ g, and the pore volume of this catalyst prepared is 0.05-0.5cm
3/ g, preferred 0.1-0.4cm
3/ g.Preferably, the bore dia of the catalyst of preparation is at least 10nm, preferred 18nm.
The present invention extends to and carries out F-T synthesis reaction to produce the method for fischer-tropsch wax, the method comprises in the fischer-tropsch reactor be supplied to by H2 and CO containing supported cobalt catalysts, except dewax product stream from reactor, and employing makes catalyst regeneration according to the renovation process in aforementioned claim described in any one.
Preferably, the catalyst of regeneration is incorporated in reactor again.
Therefore, preferably, react for phase reaction, wherein, reactant is gaseous state, and product is liquid at least partly and catalyst is solid, and carries out in slurry bubble bed bioreactor.Preferably, by H
2be supplied in the slurry in reactor with CO, described pulp bales is containing catalyst, and this catalyst is suspended in containing H
2with in the liquid of the product of CO, at least partly by being supplied to the motion of the gas in slurry, catalyst is made to keep being suspended in slurry.
Reaction temperature can at 190-260 DEG C, and within the scope of preferred 210-240 DEG C, and pressure can cling at 10-70, within the scope of preferred 20-40 bar.Be fed to the H of the gas of reactor
2/ CO ratio can at 0.5-2.2, and within the scope of preferred 1.2-1.95, and superficial gas velocity can at 5-60cm/s, within the scope of preferred 20-40cm/s.Product can experience various post-processing operation, such as, filter, dewax, hydroisomerization and/or hydrocracking.
Usually, experience is worn and torn along with passing of time by the catalyst granules of operation in the FT-reactor (particularly fluid bed or slurry bubbling bed).Wearing and tearing can be described as by the shearing force in reactor, collide, wait the physical abrasion of the particle caused with other particle or reactor internal components.Can fine grained be produced by wear surface, but division or the crushing of larger cut and particle also can occur.Chemical abrasion also can be important factor, such as, along with the catalyst granules that passes of time weakens.In FT-operation, produce steam, acidic components (such as CO
2) and a small amount of organic acid formed can cause these chemical attacks.Therefore, usually, wearing and tearing cause the thin catalyst granules of some ratio as a part for the catalyst of any inactivation.After regeneration, these fine graineds in reactor again load be not useful usually.In slurry operations, preferably be reduced at the content of the thin catalyst granules to be recharged lower than the fraction of 20 μm and be less than 3 % by weight, content preferably lower than the fraction of 10 μm is less than 0.5 % by weight, is most preferably less than 0.2 % by weight at the content of the fraction lower than 10 μm.
Detailed description of the invention
The present invention can adopt and put into practice in various manners, will illustrate in the following non-limiting examples now.
In an embodiment, all catalyst tests carry out in the fixture bed experiment chamber device with four parallel fixed bed reactors.About 1g catalyst granules (new or regenerate after calcining step, size fraction is 53-90 micron) is mixed with 20g inertia SiC.Under 350 DEG C and 1 bar, in hydrogen, carry out in-situ reducing 16 hours.Fischer-Tropsch performance step is subsequently carried out in the hydrogen of 2:1 ratio and the mixture of CO.Under 210 DEG C and 20 bar gross pressures, after flowing upper 20 hour, regulate air speed, to obtain the level of conversion of the CO of the estimation of 45-50% after 100 hours.It is highly important that and carry out selective and expression activitiy under the conversion ratio of phase same level, because the level of the steam produced in the reaction has far-reaching influence for catalyst performance.In Embodiment C, use modification procedure, wherein, directly fill in test reactor with what cross with the catalyst exhausted, and some catalyst exposure are calcined in original position.
Except C2-O oxide catalyst precursor, all embodiments relate to containing at least some reproducibility and active cobalt metal and are included in the FT catalyst in wax.For catalyst that is freshly prepd and reduction, deliberately add wax and be again oxidized to avoid cobalt between transport and storage life.For with cross with the catalyst of inactivation, wax is the heavy product fraction of the FT reaction be included in slurry-phase reactor itself, therefore, is the natural constituents of the catalyst of off-load.Wax can catalyst filling particle hole, between the assembly (agglomerate) of interval or complete covering catalyst particle.The catalyst of inactivation is from the longtime running of half industrial slurry types FT-equipment.
Embodiment A
Except dewax and calcining
Drain to allow wax by extracting funnel filling sample to Soxlet and in atmosphere sample is heated to 85 DEG C, reduce the amount of the wax be included in used catalyst particle and between used catalyst particle.Subsequently sample is transferred to ceramic crucible, and calcines 16 hours in atmosphere in the kiln of 300 DEG C.Some results are shown in table 1, comprise the identical step of the catalyst sample being applied to the new reduction be included in FT-wax, for comparing.Sample is expressed as follows:
C1-R: by the oxide catalyst on gamma-aluminium oxide carrier of reduction experience activation in hydrogen.
C2-O: the oxide catalyst on spinel type carrier.
C2-R: by the oxide catalyst on spinel type carrier of reduction experience activation in hydrogen.
C2-U1 to C2-U4: in slurry bubble bed bioreactor, in the wax of Fischer-Tropsch test deriving from extension, the catalyst of the continuous use on spinel type carrier.
Table 1. wax drains and calcines
* the gross weight mixed with wax.
* is at 500 DEG C instead of calcine at 300 DEG C.
* * uses 50,/50 % by weight cyclohexane normal heptane extraction to remove dewax instead of to drain.
* * * uses 100% normal heptane extraction to remove dewax instead of to drain.
* * * * roughly.Assuming that all carbonaceous materials are by calcining removing.
Na: data are unavailable.
Be reduced to compared with in the of 21.3% with the weight of the sample (C2-U3) by mistake, be reduced to 53.6% by the weight draining new sample (C2-R).When this mainly reflects the sample of taking when the bottom of the reactor sample from sedimentation in a reservoir, the concentration of catalyst granules in wax.New catalyst C2-R calcines further and obtains 24.2% weight reduction, and used catalyst obtains about 15% reduction (C2-U3).When calcining, the loss in weight of small part may be coke owing to accumulating during operation instead of wax.For C2-U2 sample, directly calcining without any when initially draining.Compared with 300 DEG C, at 500 DEG C, calcining obtains weight reduction.It should be noted that, due to for cross sample, when calcining, the loss in weight of remnants is only 3.4 and 4.3 % by weight (C2-U3*** and C2-U4****), and for new sample (C2-R), the remaining loss in weight is 1.5 % by weight, can remove more wax by using solvent from sample.Numeral for used catalyst also reflects the higher limit of coke content.
Embodiment B
Active testing
As described separately, in workbench-scale fixed bed reactors, testing catalytic is active.After flowing upper 100 hour under about 45% conversion ratio, compare data.
Table 2. active testing *
| Catalyst | Wax drains | Calcining | Relative activity | Relative C5+ is selective |
| C2-O | - | - | 0.96 | 0.918 |
| C2-R | Be | No | 0.87；0.91 | 0.924；0.925 |
| C2-R | Be | Be | 0.90 | 0.942 |
| C2-U1 | Be | No | 0.66 | 0.950 |
| C2-U1 | Be | Be | 0.88；0.89 | 0.965；0.963 |
| C2-U2 | No | Be | 0.82 | 0.975 |
| C2-U2-250** | No | Be | 0.74 | 0.960 |
| C2-U2-400** | No | Be | 0.68 | 0.959 |
| C2-U2-500** | No | Be | 0.65 | 0.963 |
| C2-U2*** | Solvent | No | 0.44 | 0.920 |
| C2-U2*** | Solvent | Be | 0.94 | 0.977 |
| C2-U3 | Be | No | 0.48 | 0.899 |
| C2-U3 | Be | Be | 0.83；0.86 | 0.970；0.974 |
| C2-U3*** | Solvent | Be | 1.06 | 0.962 |
| C2-U4 | Be | Be | 0.87 | 1.26 |
| C2-U4*** | Solvent | Be | 1.00 | 0.963 |
The repeatability of the fixed bed test of the sample draining and calcine that two the value displays * provided in given entry are identical.
* calcines at 250,400 or 500 DEG C.
* * uses 50,/50 % by weight cyclohexane normal heptane extraction to remove dewax instead of to drain.
See C2-U1 and C2-U3 sample, after the catalyst of calcining inactivation, relative catalyst activity existence significantly improves: respectively from 0.66 to 0.88/0.89 with from 0.48 to 0.83/0.86.When loading in the reactor, recover the most of initial relative activity of 0.90 of the catalyst of new reduction.Owing to expecting that the richness of carbon is deposited as the main cause of inactivation, current simple method effectively can remove at least very most of of this deposition.At 400 or 500 DEG C, calcining seems too high, because expection will cause active cobalt metal particle to sinter.250 DEG C have positive impact to activity, but 300 DEG C more effective.Owing to there is not Carbon deposition on new catalyst, do not affect upon calcination.
Also can be observed, catalyst C2-U1 and C2-U3 not experiencing calcining has low activity.Although reach 16 hours by hydrogen treat at 350 DEG C.Therefore, seeming hydrogen treat makes not to be effective in catalyst regeneration, and these results are used as comparative example really.In fact, when observing in the long-term slurry experiment that inactivation occurs, for identical sample, the activity of about 0.63 and 0.48 is only appropriate higher than initial activity.
Use solvent to remove dewax before calcination, for activity and selectivity, all there is very active influence.In fact, relative activity has been increased to the level (be 1.06 for C2-U2, be 1.00 for C2-U4) of the catalyst (C2-R) higher than new load.
Significant impact is, when calcining the catalyst of inactivation, towards the selectivity modification of C5+ product to 0.959-0.975 relative selectivity scope, improves about 4% relative to new catalyst.Such raising has significant impact by the product yield of GTL equipment selective.Compared with only draining, the application of new catalyst (C2-R) is drained and calcining seems not improve activity, and on optionally affecting appropriateness.Seem that the positive impact of method described herein is characteristic that is that used and catalyst that is inactivation.
Embodiment C
Original position calcining and active testing
Under 300 DEG C and 1 bar, in fixed bed reactors, carry out original position calcine 16 hours, use the heating rate of 2 DEG C/min and the air velocity of 250ml/ minute, then standard restoration and FT test.
The active testing that table 3. uses original position to calcine in fixed bed reactors
| Catalyst | Wax drains | Calcining | Relative activity | Relative C5+ is selective |
| C2-U1 | Be | Nothing | 0.66 | 0.950 |
| C2-U1 | Be | Outside device | 0.88/0.89 | 0.965/0.963 |
| C2-U1 | Be | Original position | 0.98 | 0.925 |
| C2-U2 | Be | Nothing | 0.46 | 0.917 |
| C2-U2 | Be | Outside device | 0.82 | 0.975 |
| C2-U2 | Be | Original position * | 0.75 | 0.951 |
| C2-U3 | Be | Nothing | 0.48 | 0.899 |
| C2-U3 | Be | Outside device | 0.83/0.86 | 0.970/0.974 |
| C2-U3 | Be | Original position | 0.92 | 0.939 |
* during calcining, low-down air-flow is used.
In fixed bed test reactor, carry out regeneration calcining, the significantly actively impact on relative activity can be seen, even more obvious compared with carrying out calcining in special calcining kiln.The details of calcination condition therefore may be important.A difference between two kinds of method for calcinating is, in fixed bed, forcing air to flow through sample if having time, comprises during heating.In position during calcining, use low flow velocity not as using high flow rate effective.For original position calcined catalyst, can't see find in Embodiment B very high selective.This observation may be owing to not too effectively mixing with inertia (SiC), and because wax is remaining, before filling, catalyst granules adheres to each other.The clearly sign of restriction is spread in the labor display of data in these experiments.
Embodiment D
Porosity
Compared with new catalyst, pore volume and the surface area of regenerated catalyst are shown in table 4.
Table 4. before regeneration after pore property
| Catalyst/support | Pore volume (cm 3/g) | Surface area (cm 2/g) |
| C2-carrier | 0.27 | 55.4 |
| C2-O | 0.16 | 43.3 |
| C2-U1-calcining | 0.17 | 43.1 |
| C2-U2-calcining | 0.16 | 42.8 |
Can be observed, compared with the catalyst of the regeneration after calcining step, for new oxide catalyst, can't see the detectable change of pore volume or surface area.
Claims (69)
1. make a method for the catalyst regeneration of the inactivation from fischer-tropsch reactor, described catalyst be cobalt load on the modified aluminium oxide supports comprising Spinel, the method comprises the following steps:
-take out step, wherein, the catalyst of a part of inactivation is taken out together with liquid hydrocarbon from reactor;
-concentration step, wherein, improves the concentration of catalyst in liquid hydrocarbon at lower than the temperature of 220 DEG C, to produce with dry weight for benchmark, and the carbon monoxide-olefin polymeric of the first inactivation of the catalyst granules containing 45-99.5%;
-the first calcining step, wherein, make the carbon monoxide-olefin polymeric experience oxidizing gas of described first inactivation, at the temperature of 150-600 DEG C of scope, arrange the gaseous oxygen compound carbonaceous material be included in the catalyst of described inactivation being oxidized into the component of carbonaceous material, to produce the carbon monoxide-olefin polymeric of the second inactivation;
-reactivation step, wherein, by the carbon monoxide-olefin polymeric reactivation of described second inactivation, to produce the catalyst of regeneration.
2. method according to claim 1, wherein, described reactor is slurry bubble bed bioreactor, wherein, by H
2be supplied in the slurry in reactor with CO gas, described pulp bales is containing catalyst, and this catalyst is suspended in containing H
2with in the liquid hydrocarbon of the product of CO, at least partly by being supplied to the motion of the gas in slurry, make described catalyst keep being suspended in slurry, and described taking-up step comprise take out a part of slurry from reactor.
3. method according to claim 1 and 2 wherein, take dry weight as benchmark, is the 0.01-10 % by weight of the total quantity in stock of catalyst in the amount of taking out the catalyst taken out in step.
4. method according to claim 1 and 2 wherein, take dry weight as benchmark, is the 0.1-5 % by weight of the total quantity in stock of catalyst in the amount of taking out the catalyst taken out in step.
5. according to aforementioned method according to claim 1, wherein, carry out described concentration step, to produce the catalyst content of 70-99.5 % by weight.
6. according to aforementioned method according to claim 1, wherein, carry out described concentration step, to produce the carbon monoxide-olefin polymeric of described first inactivation of wax content in 1-55 % by weight scope.
7. according to aforementioned method according to claim 1, wherein, carry out described concentration step, to produce the carbon monoxide-olefin polymeric of described first inactivation of wax content in 2-45 % by weight scope.
8. according to aforementioned method according to claim 1, wherein, carry out described concentration step, to produce the carbon monoxide-olefin polymeric of described first inactivation of wax content in 3-30 % by weight scope.
9. according to aforementioned method according to claim 1, wherein, described concentration step comprise be selected from sedimentation, filtration, Magnetic Isolation, hydrocyclone be separated and solvent-extracted operation.
10. method according to claim 9, wherein, described in be operating as sedimentation, then remove a part of liquid hydrocarbon.
11. methods according to claim 9, wherein, described in be operating as solvent extraction, and described solvent is hydrocarbon.
12. methods according to claim 9, wherein, described in be operating as solvent extraction, and described solvent is small amount of liquids F-T product and/or paraffinic naphtha.
13. methods according to claim 11 or 12, wherein, join described solvent in hydrocyclone.
14. according to aforementioned method according to claim 1, and wherein, described concentration step carries out at lower than the temperature of 200 DEG C.
15. according to aforementioned method according to claim 2, and wherein, in the carbon monoxide-olefin polymeric of described first inactivation, the quantity of the carbon atom of hydrocarbon molecule is less than 70% of the quantity of the carbon atom of the hydrocarbon molecule in slurry-phase reactor.
16. methods according to claim 15, wherein, described quantity is the 25-50% of the quantity of the carbon atom of hydrocarbon molecule in slurry-phase reactor.
17. according to aforementioned method according to claim 1, and wherein, in the first calcining step, described oxidizing gas is oxygen-containing gas.
18. according to aforementioned method according to claim 1, and wherein, in the first calcining step, described oxidizing gas is air.
19. methods according to claim 17 or 18, wherein, the oxygen content of described oxygen-containing gas is 2-30 volume %.
20. methods according to claim 17 or 18, wherein, the oxygen content of described oxygen-containing gas is 5-21 volume %.
21. according to aforementioned method according to claim 1, and wherein, described first calcining step comprises the carbon monoxide-olefin polymeric of described first inactivation is delivered to calcining furnace, and described calcining furnace has the temperature of at least 150 DEG C.
22. according to aforementioned method according to claim 1, and wherein, described first calcining step comprises the carbon monoxide-olefin polymeric of described first inactivation is delivered to calcining furnace, and described calcining furnace has the temperature of at least 250 DEG C.
23. according to aforementioned method according to claim 1, and wherein, described first calcining step carries out at the maintenance temperature of 150-600 DEG C.
24. according to aforementioned method according to claim 1, and wherein, described first calcining step carries out at the maintenance temperature of 250-400 DEG C.
25. according to aforementioned method according to claim 1, and wherein, the time that described first calcining step carries out is at 0.01-10 hours window.
26. according to aforementioned method according to claim 1, and wherein, the time that described first calcining step carries out is at 0.1-2 hours window.
27. according to aforementioned method according to claim 1, and wherein, described first calcining step carries out in rotary calciner, static kiln or fixed bed or fluid bed.
28. according to aforementioned method according to claim 1, wherein, carries out described first calcining step, and arranges so that the content of the carbonaceous material in catalyst is reduced to <1 % by weight.
29. according to aforementioned method according to claim 1, and wherein, the method comprises: the second calcining step, and described second calcining step operates at higher than the maintenance temperature of the first calcining step.
30. according to aforementioned method according to claim 1, and wherein, described reactivation step comprises the process of use reducing gas.
31. methods according to claim 30, wherein, described reducing gas contains hydrogen.
32. according to aforementioned method according to claim 1, wherein, carries out at one or more maintenance temperature of described reactivation step within the scope of 200-600 DEG C.
33. according to aforementioned method according to claim 1, wherein, carries out at one or more maintenance temperature of described reactivation step within the scope of 250-500 DEG C.
34. according to aforementioned method according to claim 1, wherein, carries out at one or more maintenance temperature of described reactivation step within the scope of 300-450 DEG C.
35. according to aforementioned method according to claim 1, wherein, after reactivation step, is again incorporated in reactor by the catalyst of regeneration.
36. methods according to claim 35, wherein, before being again incorporated into by the catalyst of regeneration in reactor, mix the catalyst of described regeneration with liquid hydrocarbon.
37. methods according to claim 35, wherein, before being again incorporated into by the catalyst of regeneration in reactor, mix the catalyst of described regeneration with fraction F-T product.
38. methods according to claim 35, wherein, before being again incorporated into by the catalyst of regeneration in reactor, after remove most of catalyst granules from slurry, mix the catalyst of described regeneration with the liquid hydrocarbon taken out as slurry from reactor.
39. methods according to claim 35, wherein, regeneration and the ratio being back to the catalyst of the taking-up of reactor is at least 60%.
40. methods according to claim 35, wherein, regeneration and the ratio being back to the catalyst of the taking-up of reactor is at least 80%.
41. methods according to claim 35, wherein, in the residence time destribution of the catalyst granules of described regeneration, the catalyst inventory of 80% uses the time period of 1 week-10 years in the reactor.
42. methods according to claim 35, wherein, in the residence time destribution of the catalyst granules of described regeneration, the catalyst inventory of 80% uses the time period of 1 month-5 years in the reactor.
43. methods according to claim 35, wherein, in the residence time destribution of the catalyst granules of described regeneration, the catalyst inventory of 80% uses the time period of 2 months-2 years in the reactor.
44. methods according to claim 35, wherein, the method also comprises the step by using filter, net or sieve to be reduced in the level of fines in the catalyst of regeneration in the gas flow, comprises and uses fluid bed or air screening installation.
45. methods according to claim 35, wherein, in the catalyst of the regeneration again introduced, the content lower than the thin catalyst granules of the fractions of 20 μm is less than 3 % by weight.
46. methods according to claim 35, wherein, in the catalyst of the regeneration again introduced, the content lower than the thin catalyst granules of the fractions of 10 μm is less than 0.5 % by weight.
47. methods according to claim 35, wherein, in the catalyst of the regeneration again introduced, the content lower than the thin catalyst granules of the fractions of 10 μm is less than 0.2 % by weight.
48. according to aforementioned method according to claim 1, and wherein, before use cobalt initial impregnation, described catalyst support material is gama-alumina.
49. methods according to claim 48, wherein, use 2-valency source metal to flood described gama-alumina, and calcine, to form Spinel.
50. methods according to claim 49, wherein, described 2-valency metal is nickel or zinc, and its amount is greater than 5 % by weight of the catalyst of final reduction.
51. methods according to claim 49, wherein, described 2-valency metal is nickel or zinc, and its amount is greater than 10 % by weight of the catalyst of final reduction.
52. methods according to claim 49 or 50 or 51, wherein, carry out at the temperature of described spinelle calcining within the scope of 900 DEG C-1250 DEG C.
53. according to aforementioned method according to claim 1, and wherein, after regeneration, in the cobalt content of the catalyst of described regeneration, the no more than amount of 5 % by weight is different from the new catalyst after reduction.
54. according to aforementioned method according to claim 1, and wherein, after regeneration, in the cobalt content of the catalyst of described regeneration, the amount being less than 2 % by weight is different from the new catalyst after reduction.
55. according to aforementioned method according to claim 1, and wherein, after regeneration, in the cobalt content of the catalyst of described regeneration, the amount being less than 0.5 % by weight is different from the new catalyst after reduction.
56. according to aforementioned method according to claim 1, and wherein, described catalyst contains promoter.
57. methods according to aforementioned claim 56, wherein, described promoter is rhenium or platinum.
58. according to aforementioned method according to claim 1, wherein, after firing still before reduction, comprises the specific area of the oxide catalyst of the preparation of the cobalt oxide on modified support up to 150m
2/ g or up to 80m
2/ g.
59. according to aforementioned method according to claim 1, and wherein, the new and pore volume of the catalyst of regeneration of described oxide form is 0.05-0.5cm
3/ g.
60. according to aforementioned method according to claim 1, and wherein, the new and pore volume of the catalyst of regeneration of described oxide form is 0.1-0.4cm
3/ g.
61. according to aforementioned method according to claim 1, wherein, before recycling, and the coating protection of the catalyst wax of described regeneration.
62. 1 kinds are carried out F-T synthesis reaction to produce the method for fischer-tropsch wax, and wherein, the method comprises H
2be supplied in the fischer-tropsch reactor containing supported cobalt catalysts with CO, except dewax product stream from reactor, and employing makes catalyst regeneration according to the renovation process in aforementioned claim described in any one.
63. methods according to claim 62, wherein, are incorporated in reactor again by the catalyst of described regeneration.
64. methods according to claim 62 or 63, wherein, described reaction temperature is within the scope of 190-260 DEG C, and reaction pressure is within the scope of 10-70 bar.
65. method according to claim 62, wherein, the H of the gas of fischer-tropsch reactor is supplied to described in
2/ CO ratio is within the scope of 0.5-2.2.
66. methods according to claim 62, wherein, superficial gas velocity is within the scope of 5-60cm/s in the reactor.
67. method according to claim 62, wherein, the product of described F-T synthesis reaction experiences post processing subsequently.
68. methods according to claim 67, wherein, described post processing is selected from dewaxing, hydroisomerization, hydrocracking and these combination.
The purposes of catalyst in Fiscber-Tropscb synthesis process of regeneration prepared by the method in 69. claim 1-61 described in any one.
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| GB1013924.4A GB2482905B (en) | 2010-08-19 | 2010-08-19 | Fischer-tropsch catalyst regeneration |
| GB1013924.4 | 2010-08-19 | ||
| PCT/GB2011/001230 WO2012022942A1 (en) | 2010-08-19 | 2011-08-17 | Fischer-tropsch catalyst regeneration |
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| WO2014144855A2 (en) * | 2013-03-15 | 2014-09-18 | Gi-Gasification International(Luxembourg) S.A. | Methods, systems and apparatuses for fischer-tropsch catalyst regeneration |
| WO2015025225A2 (en) * | 2013-08-21 | 2015-02-26 | Saudi Basic Industries Corporation | A process for the production of hydrocarbons |
| CN105080570B (en) * | 2014-05-14 | 2017-10-27 | 中国石油化工股份有限公司 | Fluid bed syngas directly prepares the renovation process of low-carbon alkene ferrum-based catalyst |
| US9233360B1 (en) * | 2014-09-10 | 2016-01-12 | Chevron U.S.A. Inc. | Stable support for Fischer-Tropsch catalyst |
| US10190057B2 (en) | 2014-11-20 | 2019-01-29 | Sasol Technology Proprietary Limited | Fischer-tropsch synthesis |
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| CN108348911B (en) * | 2015-11-23 | 2021-07-06 | 科莱恩公司 | Process for regenerating a catalyst useful in a fischer-tropsch process |
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| CN111921459B (en) * | 2020-07-31 | 2022-04-08 | 宁波巨化化工科技有限公司 | Reactor capable of simultaneously producing trichloroethylene and tetrachloroethylene |
| KR102411339B1 (en) * | 2020-10-20 | 2022-06-20 | 한국화학연구원 | Fischer-Tropsch synthesis catalyst regeneration method |
| CN115041194B (en) * | 2021-03-08 | 2024-01-30 | 国家能源投资集团有限责任公司 | Method for regenerating Fischer-Tropsch synthesis catalyst |
| CN115178303B (en) * | 2021-04-02 | 2024-05-24 | 绍兴绿奕化工有限公司 | Method for recovering waste porous catalyst |
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| CN1620411A (en) * | 2002-01-29 | 2005-05-25 | 埃克森美孚研究工程公司 | Fischer-tropsch catalyst enhancement |
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| PL2606104T3 (en) | 2017-11-30 |
| US8921252B2 (en) | 2014-12-30 |
| EP2606104A1 (en) | 2013-06-26 |
| GB201013924D0 (en) | 2010-10-06 |
| WO2012022942A1 (en) | 2012-02-23 |
| GB2482905B (en) | 2016-01-13 |
| CN103140570A (en) | 2013-06-05 |
| US20130210939A1 (en) | 2013-08-15 |
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